Appendix D. Special Types of Reactive Chemicals
Reactivity information is from R. W. Johnson, S. W. Rudy, and S. D. Unwin, Essential Practices for Managing Chemical Reactivity Hazards (New York, NY: American Institute of Chemical Engineers, 2003).
Table AD-1 A Few Pyrophoric and Spontaneously Combustible Categories and Chemicals (Note: These materials combust on exposure to air.)
Category |
Examples |
|---|---|
Finely divided metals (without oxide film) |
Aluminum, calcium, cobalt, iron, magnesium, manganese, palladium, platinum, titanium, tin, zinc, zirconium |
Many hydrogenation catalysts containing adsorbed hydrogen (before and after use) |
Raney nickel catalyst with adsorbed hydrogen |
Alkali metals |
Potassium, sodium |
Metal hydrides |
Germane, lithium aluminum hydride, potassium hydride, sodium hydride |
Partially or fully alkylated metal hydrides |
Butyllithium, diethylaluminum hydride, triethylbismuth, trimethylaluminum |
Arylmetals |
Phenylsodium |
Alkylmetal derivatives |
Diethylethoxyaluminum, dimethylbismuth chloride |
Analogous derivatives of nonmetals |
Diborane, dimethylphosphine, phosphine, triethylarsine |
Carbonylmetals |
Pentacarbonyliron, octacarbonyldicobalt |
Grignard reagents (RMgX) |
Ethylmagnesium chloride, methylmagnesium bromide |
Metal sulfides |
Iron sulfide |
Miscellaneous |
Phosphorus (white), titanium dichloride |
Table AD-2 Some Chemical Structures Susceptible to Peroxide Formation (Note: The peroxides formed may become unstable and explode when disturbed.)
Chemical structure (not all bonds are shown) |
Examples/explanation |
|---|---|
Organic substances |
|
CH2–O–R |
Ethers with alpha hydrogen atoms, especially cyclic ethers and those containing primary and secondary alcohol groups, form dangerously explosive peroxides on exposure to air and light |
CH(–O–R)2 |
Acetals with alpha hydrogen atoms |
C=C–CH |
Allyl compounds (olefins with allylic hydrogen atoms), including most alkenes |
C=C–X |
Halo-olefins (e.g., chloroolefins, fluoroolefins) |
C=CH |
Vinyl and vinylidene esters, ethers, styrenes |
C=C–C=C |
1,3-Dienes |
C=CH–C–CH |
Alkylacetylenes with alpha hydrogen atoms |
C=CH–C=CH |
Vinylacetylenes with alpha hydrogen atoms, tetrahydronaphthalenes |
(R)2CH–Ar |
Alkylarenes with tertiary hydrogen atoms (e.g., cumene) |
(R)3CH |
Alkanes and cycloalkanes with tertiary hydrogen atoms (e.g., t-butane, isopropyl compounds, decahydronaphthalenes) |
C=CH–CO2R |
Acrylates, methacrylates |
(R)2CH–OH |
Secondary alcohols |
O=C(R)–CH |
Ketones with alpha hydrogen atoms |
O=CH |
Aldehydes |
O=C–NH–CH |
Substituted ureas, amides, and lactams that have a hydrogen atom on a carbon atom attached to nitrogen |
CH–M |
Organometallic compounds with a metal atom bonded to carbon |
|
Inorganic substances |
Alkali metals, especially potassium, rubidium, and cesium |
|
Metal amides (e.g., NaNH2) |
|
Metal alkoxides (e.g., sodium t-butoxide) |
|
Table AD-3 Chemical Categories Susceptible to Water Reactivity
Category |
Examples |
|---|---|
Alkali and alkaline-earth metals |
Calcium, potassium, sodium, lithium |
Anhydrous metal halides |
Aluminum tribromide, germanium tetrachloride, titanium tetrachloride |
Anhydrous metal oxides |
Calcium oxide |
Chlorosilanes |
Methyldichlorosilane, trichlorosilane, trimethylchlorosilane |
Epoxides (e.g., with acid present) |
Butylene oxide, ethylene oxide, diepoxy butane, epibromohydrin |
Finely divided metals, no oxide film |
Aluminum, cobalt, iron, magnesium, titanium, tin, zinc, zirconium |
Grignard reagents; organometallics |
Ethylmagnesium chloride, methylmagnesium bromide |
Inorganic acid halides |
Phosphoryl chloride, sulfuryl chloride, chlorosulfuric acid |
Inorganic cyanides |
Barium cyanide, calcium cyanide, cyanogen chloride, silver cyanide |
Isocyanates |
n-Butyl isocyanate, methyl isocyanate, toluene diisocyanate |
Metal alkyls |
Aluminum alkyls, lithium alkyls |
Metal amides |
Lead amide, potassium amide, silver amide, sodium amide |
Metal hydrides |
Calcium hydride, lithium aluminum hydride, sodium borohydride |
Nitrides, phosphides, carbides |
Aluminum phosphide, calcium carbide, gallium phosphide |
Nonmetal hydrides |
Boron trifluoride, phosphorus trichloride, silicon tetrachloride |
Nonmetal oxides |
Phosphorus pentoxide, sulfur trioxide |
Organic acid halides/anhydrides |
Acetic anhydride, acetyl chloride |
Table AD-4 Common Water-Reactive Chemicals (Note: This is not an exhaustive list. Reaction with water may be slow to violent. Reaction products may be toxic, corrosive, or flammable. Products may be gaseous and of sufficient quantity to rupture unrelieved containment.)
Acetic anhydride |
Acetyl chloride |
Alkylaluminums |
Allyl trichlorosilane |
Aluminum chloride, anhydrous |
Aluminum phosphide |
Amyl trichlorosilane |
Benzoyl chloride |
Boron tribromide |
Boron trifluoride |
Boron trifluoride etherate |
Bromine pentafluoride |
Bromine trifluoride |
n-Butyl isocyanate |
Butyllithium |
Butyric anhydride |
Calcium |
Calcium carbide |
Chlorine trifluoride |
Chlorosilanes |
Chlorosulfonic acid |
Chromium oxychloride |
Cyanamide |
Decaborane |
Diborane |
Dichloroacetyl chloride |
Dichlorosilane |
Diethylaluminum chloride |
Diethylaluminum hydride |
Diethyl carbamyl chloride |
Diethyl telluride |
Diethylzinc |
Diisobutylaluminum hydride |
Dimethyldichlorosilane |
Diphenyldichlorosilane |
Dipropylaluminum hydride |
Ethylaluminum dichloride |
Ethylaluminum sesquichloride |
Ethyldichlorosilane |
Ethyltrichlorosilane |
Fluorine |
Gallium arsenide |
Gallium phosphide |
Germane |
Isobutyric anhydride |
Isophorone diisocyanate |
Lithium |
Lithium aluminum hydride |
Lithium hydride |
Methyl isocyanate |
Methylaluminum sesquibromide |
Methylaluminum sesquichloride |
Methyldichlorosilane |
Methylene diisocyanate |
Methylpentaldehyde |
Methyltrichlorosilane |
Monochloro-s-triazinetrione acid |
Mono-(trichloro)-tetra (mono-potassium dichloro)-penta-s-triazinetrione, dry |
Octadecyltrichlorosilane |
Phenyl trichlorosilane |
Phosphorus oxychloride |
Phosphorus pentachloride |
Phosphorus pentasulfide |
Phosphorus tribromide |
Phosphorus trichloride |
Potassium |
Potassium–sodium alloys |
Propionyl chloride |
Silicon tetrachloride |
Silicon tetrafluoride |
Sodium |
Sodium dichloro-s-triazinetrione dihydrate |
Sodium hydride |
Sodium hydrosulfite |
Sulfur chlorides |
Sulfuric acid |
Sulfuryl chloride |
Tetraethyl lead |
Tetramethyl lead |
Thionyl chloride |
Titanium tetrachloride |
Toluene diisocyanate |
Trichlorosilane |
Triethylaluminum |
Triethylborane |
Triisobutylaluminum |
Trimethylaluminum |
Trimethylchlorosilane |
Tripropyl aluminum |
Vanadium tetrachloride |
Vinyl trichlorosilane |
Zirconium tetrachloride |
Table AD-5 Typical Oxidizers
Ammonium dichromate |
Ammonium nitrate |
Ammonium perchlorate |
Ammonium permanganate |
Ammonium persulfate |
Amyl nitrate |
Barium bromate |
Barium chlorate |
Barium hypochlorite |
Barium perchlorate |
Barium permanganate |
Barium peroxide |
Bromine pentafluoride |
Bromine trifluoride |
1-Bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) |
Calcium chlorate |
Calcium chlorite |
Calcium hypochlorite |
Calcium perchlorate |
Calcium permanganate |
Calcium peroxide |
Chloric acid (10% maximum concentration) |
Chlorine |
Chlorine trifluoride |
Chlorosulfonic acid |
Chromium trioxide (chromic acid) |
Copper chlorate |
Guanidine nitrate |
Halane (1,3-dichloro-5,5-dimethylhydantoin) |
Hydrogen peroxide solutions |
Lead dioxide |
Lead perchlorate |
Lithium chlorate |
Lithium hypochlorite |
Lithium perchlorate |
Lithium peroxide |
Magnesium bromate |
Magnesium chlorate |
Magnesium perchlorate |
Magnesium peroxide |
Manganese dioxide |
Mercurous chlorate |
Monochloro-s-triazinetrione acid |
Mono-(trichloro)-tetra-(monopotassium dichloro)-penta-s-triazinetrione |
Nitric acid and fuming nitric acid |
Nitrites, inorganic |
Nitrogen oxides (NOx) |
Oxygen |
Peracetic acid |
Perchloric acid solutions |
Potassium bromate |
Potassium chlorate |
Potassium dichloro-striazinetrione (potassium dichloroisocyanurate) |
Potassium dichromate |
Potassium percarbonate |
Potassium perchlorate |
Potassium permanganate |
Potassium peroxide |
Potassium persulfate |
Potassium superoxide |
n-Propyl nitrate |
Silver peroxide |
Sodium bromate |
Sodium carbonate peroxide |
Sodium chlorate |
Sodium chlorite |
Sodium dichloro-striazinetrione (sodium dichloroisocyanurate) |
Sodium dichloro-s-triazinetrione dihydrate |
Sodium dichromate |
Sodium perborate (anhydrous) |
Sodium perborate monohydrate |
Sodium perborate tetrahydrate |
Sodium percarbonate |
Sodium perchlorate |
Sodium perchlorate monohydrate |
Sodium permanganate |
Sodium peroxide |
Sodium persulfate |
Strontium chlorate |
Strontium perchlorate |
Strontium peroxide |
Tetranitromethane |
Thallium chlorate |
Trichloro-s-triazinetrione (trichloroisocyanuric acid all forms) |
Urea hydrogen peroxide |
Zinc bromate |
Zinc chlorate |
Zinc permanganate |
Zinc peroxide |
Table AD-6 Some Polymerizing Compounds (Note: These chemicals may polymerize rapidly with release of large amounts of heat.)
Acrolein |
Acrylamide |
Acrylic acid |
Acrylonitrile |
1,3-Butadiene |
Butylacrylate |
1,2-Butylene oxide |
Butyraldehyde |
Crotonaldehyde |
Dichloroethylene |
Diketene |
Divinylbenzene |
Epichlorohydrin |
Ethyl acrylate |
Ethylene |
Ethylene cyanohydrin |
Ethyleneimine |
Ethylene oxide |
2-Ethylhexylacrylate |
Hydrogen cyanide |
Isoprene |
Methacrylic acid |
Methyl acrylate |
Methylchloromethyl ether |
Methyl isocyanate |
Methyl methacrylate |
Methyl vinyl ketone |
Propargyl alcohol |
Propionaldehyde |
Propylene oxide |
Styrene |
Tetrafluoroethylene |
Tetrahydrofuran |
Toluene diisocyanate |
Trimethoxysilane |
Vinyl acetate |
Vinyl acetylene |
Vinyl chloride |
Vinyl ether |
Vinylidene chloride |
Vinyl toluene |